Epoxy ether compositions



United States Patent 3,035,001 EPOXY ETHER COMPOSITIONS Samuel W. Tinsley, South Charleston, Paul S. Starcher, Charleston, and Charles W. McGary, Jr., and Charles T. Patrick, In, South Charleston, W. Va., assignors to gnilcin Carbide Corporation, a corporation of New or No Drawing. Filed May 31, 1960, Ser. No. 32,512 24 Claims. (Cl. 260-20) This invention relates to epoxy ether compositions. In one aspect, this invention relates to a method for preparing bis(3-oxatetracyclo[4.4.0.I .O ]undec-8-yl) ether, In various other aspects, this invention relates to curable, polymerizable compositions comprising bis (3-oxatetracyclo[4.4.0.1 .0 ]undec-8-yl) ether and an active organic hardener, to the thermosetting intermediate reaction products, and to the cured, polymerized products resulting therefrom.

The polymerizable compositions of the invention can be readily handled in resin-forming operations such as coating, laminating, bonding, molding, casting, potting, and the like. These polymerizable compositions are capable of accepting solid materials, such as fillers and pigments, for providing various effects in physical properties and coloration. With or without such added solid materials, the polymerizable compositions can be made to fill small intricacies of molds without the necessity of applying high pressures or heating to high temperatures, although such measures can be employed, if desired. The polymerizable compositions also can be easily spread, brushed, or sprayed by many techniques available in the paint, lacquer, and varnish industries for making coatings and finishes. Little, if any, shrinkage occurs in curing to the resin. The polymerizable compositions are capable of being accurately shaped by molds having intricate molding surfaces and fully cured to resins carrying exact details of such molding surfaces. They can be also advantageously employed in the potting of such fragile articles as electronic components.

The curable, polymerizable compositions of the invention also can be partially reacted at elevated temperatures to form viscous thermosetting liquids or thermosetting solids. The resulting thermosetting intermediate reaction products can be dissolved in an inert normallyliquid organic medium and applied as heat-curable coatings. To aid solution, the thermosetting solid products can be powdered or granulated, if desired. The thermo setting solids also can be used as molding powder compositions which can be converted to fully cured solid products by the application of heat and/or pressure. Numerous other uses, applications, and unexpected advantages and results will become apparent upon a consideration of the various embodiments of the invention which are discussed hereinafter.

Accordingly, one or more of the following objects will be achieved by the practice of the invention.

It is an object of the invention to prepare novel curable, partially cured, and cured compositions comprising bis(3- oxatetracyclo [4.4.0.1' .0 undec-8-yl) ether and an active organic hardener. It is another object of the invention to prepare novel curable, polymerizable compositions comprising bis(3 oxatetracyclo[4.4.O.I .O ]Undec- 8-yl) ether, an active organic hardener, and a modifying amount of a different active organic compound to thereby impart special and desirable characteristics and properties to ultimately, fully cured compositions. It is a further object of the invention to prepare novel curable compositions and partially cured compositions (thermo setting intermediate reaction products) comprising bis(3- oxatetracyclo [4.4.0.l .0 ]undec-8-yl) ether and an active organic hardener which compositions when dissolved in an inert normally-liquid organic medium are useful in the fields of coatings, laminates, adhesives, and the like. A still further object of the invention is to prepare novel thermosetting intermediate reaction solid products resulting from the partial reaction of a composition comprising bis(3 oxatetracyclo [4.4.0.l l0 undec-S- yl) ether and an active organic hardener which products are useful as molding powder compositions. Another object of the invention is to provide novel and useful high molecular weight polymeric varnish compositions which result from the homopolymerization of the hydroxyand epoxy-containing products prepared by the reaction of bis (3-oxatetracyclo [4.4.O.l .0 ]undec-8-y1) ether and an aliphatic hydrocarbon monocarboxylic acid. It is also an object of the invention to prepare novel and useful high molecular weight polymeric varnish compositions which result from the esterification of fusible, soluble polymeric polyhydric alcohols with organic fatty acids, said polymeric polyhydric alcohols being prepared by the reaction of bis(3-oxatetracyclo[4.4.0.1' .0 ]undec-8- yl) ether and a polyol. A further object of the invention is to provide novel, useful curable and cured compositions comprising bis(3 oxatetracyclo[4.4.O.1" .0 ]undec-8- yl) ether, a polyepoxide, and an active organic hardener. It is another object of the invention to prepare novel bis- (3-oxatetracyclo[4.4.0.1 .0 ]undec-S-yl) ether. A further object of the invention is to prepare homopolymerized products of bis(3-oxatetracyclo[4.4.0.1" .O ]undec- 8-yl) ether. Numerous other objects will become apparent to those skilled in the art from a consideration of the disclosure.

In a broad aspect, the invention pertains to the novel and useful bis(3-oxatetracyclo[4.4.0.l' .O ]undec-S- yl) ether corresponding to the formula:

Bis(3 oxatetracyclo [4.4.O.1" .O ]undec 8 yl) ether can be prepared by the epoxidation of his (tricyclo- [4.3.0.1 ]-7-decen-3-yl) ether with organic peracids. Bis(tricyclo[4.3.0.1 ]-7-decen-3-yl) ether is reacted with a solution of peracid, e.g., perbenzoic acid, perpropionic acid, peracetic acid, and the like, in an inert normallyliquid organic medium such as ethyl acetate, acetone, butyl acetate and the like at a temperature in the range from about 0 C. to about 100 C., preferably from about 25 C. to about C., for a period of time sufiicient to introduce oxirane oxygen at the site of all of the carbon to carbon double bonds of the olefinic ether. The quantity of peracid consumed during the epoxidation reaction can be readily determined during the course of the reaction by Well-known procedures. A residence time of from about several minutes to 18 hours, is satisfactory in most instances. Theoretically, to eifect substantially complete epoxidation of the bis(tricyclo [4.3.O.l ]-7-decen-3-y1) ether, at least a stoichiometric quantity of peracetic acid per carbon to carbon double of the ether should be employed. The inert-normally liquid organic vehicle and acetic acid by-product can be recovered from the reaction product mixture, for example, by distillation under reduced pressure. If desired, the residue product can be subjected to fractional distillation, crystallization, and the like to obtain the epoxy ether product in high purity.

In various embodiments, the invention is further directed to novel curable, partially cured, and cured compositions comprising the novel epoxy ether characterized V by Formula I supra and an active organic hardener. The active organic hardeners illustrated hereinafter are employed in a curing amount, that is, an amount which is sufiicient to cause the curable system comprising the epoxy ether to become a thermosetting or thermoset resin in accordance with the teachings of the instant specification. Representative active organic hardeners include polycarboxylic acids, polycarboxy polyesters, polycarboxylic acid anhydrides, polyols, i.e., polyhydric phenols and polyhydric alcohols, polyfunctional amines, polythiols, polyisocyanates, polyisothiocyanates, polyacyl halides, and the like. The novel compositions can contain the epoxy ether as well as one active organic hardener or a mixture of active organic hardeners.

The curable compositions of the invention can be prepared by mixing the epoxy ether with the active organic hardener(s), preferably under agitation so as to obtain a homogeneous mixture. The order of addition of the components does not appear to be critical. When a solid or highly viscous active organic hardener is employed, heating is advantageous in facilitating the formation of a solution. In preparing homogeneous mixtures, it is advantageous to employ a temperature as high as the melting point of the highest melting component contained in the curable mixture. In any event the application of heat should not be prolonged to the extent that appreciable curing takes place.

The curable compositions of the invention can be partially cured or fully cured by maintaining the temperature in the range of from about C., and lower, to about 250 C., and higher, and preferably from about 25 to about 200 C. A higher curing temperature generally will provide a thermosetting or thermoset resin in less time than a lower curing temperature. One preferable method is to heat the curable compositions to a temperature Within the range from about 50 C. to 150 C. to first partially cure the composition. A temperature from about 100 C. to 200 C. then can be used to complete the cure. However, any one or combination of two or more temperatures within the specified range of 10 C. to 250 C. can be employed, if desired, to eifect the full cure. For casting purposes, the preferred minimum temperature of the normally-solid curable compositions is that at which said compositions form a uniform melt, Whereas the coatings and the preparation of laminates, the use of solvents will allow the use of lower temperature.

The time for eifecting the partial cure or complete cure will be governed, to an extent, on several factors such as the particular active organic hardener(s) employed, the proportions of the epoxy ether and active organic hardener, the inclusion of an active organic hardener modifier, the inclusion of a catalyst, the concentration of the catalyst and/ or modifier, the temperature for effecting the cure, and other considerations. In general, the time for effecting the complete cure can vary from several minutes to several days, e.g., from 10 minutes to one week, depending upon the correlation of such factors as illustrated above.

If desired, catalysts can be incorporated into the curable compositions of the invention to increase the cure rate and/or reduce the gelation period. It is generally suitable to add the catalyst to the curable composition which is maintained at a temperature in the range of from about 10 to 100 C. Agitation of the curable composition prior to, during, and after the incorporation of the catalyst is desirable to ensure a homogeneous mixture. If desired, higher temperatures may be employed with, the possibility, however, of inducing premature and localized curing around catalyst particles prior to the formation of a homogeneous, curable mixture. In most cases it may be desirable to obtain a homogeneous mixture before bringing about any substantial degree of curing and in such instances low mixing temperatures of the order specified above can be employed. Catalyst concentrations and curing temperatures are believed to affect the curing rate, the higher concentrations and temperatures promoting faster cures than the lower ones. Catalyst concentrations can be varied over a broad range and can be selected on the basis of the rate of cure desired and the curing temperature to be used. It has been found that catalyst concentrations from about 0.005, and lower, to 15, and higher, weight percent, preferably from about 0.01 to 5 weight percent, based on the weight of the epoxy ether component, are advantageous in forming valuable thermoset resins from the curable compositions.

Basic and acidic catalysts which can be employed in the curable compositions include, for example, the metal halide Lewis acids, e.g., boron trifluoride, aluminum chloride, zinc chloride, stannic chloride, ferric chloride, boron trifluoride-amine complex, boron trifluoride-piperidine complex, boron trifiuoride-1,6-hexanediamine complex, boron tritluoride-monoethylamine complex, boron tn'fluoride-ether complex, boron trifluoride-dimethyl ether complex, boron trifiuoride-diethyl ether complex, boron trifiuoride-dipropyl ether complex, and the like; the strong mineral acids e.g., sulfuric acid, phosphoric acid, polyphosphoric acid, perchloric acid, and the like; the saturated aliphatic hydrocarbon sulfonic acids and the aromatic hydrocarbon sulfonic acids, e.g., ethylsulfonic acid, propylsulfonic acid, benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, lower alkyl substitutedbenzenesulfonic acid, and the like; the alkali metal hydroxides, e.g., sodium hydroxide, potassium hydroxide, and the like; the amines, e.g., alpha-methylbenzyl-dimethylamine, dimethylethylamine, triethylamine, tripropylamine, trimethylammonium hydroxide, and the like. When the catalyst and curable compositions are immiscible, the catalyst can be added as a solution in an inert normally-liquid organic medium. Typical media for the catalysts include the organic ethers, e.g., diethyl ether, dipropyl ether, and the like; the organic esters, e.g., methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, and the like; the organic ketones, e.g., acetone, cyclohexanone, methylcyclohexanone, and the like.

In one preferred embodiment the invention is directed to novel curable, partially cured, and cured compositions comprising the epoxy ether and polycarboxylic acid in such relative amounts as to provide from about 0.1 to about 2.0 carboxyl groups, e.g., COOH groups, of said polycarboxylic acid per epoxy group, i.e.,

' succinic acid, glutaric acid, adipic acid, pimelic acid,

suberic acid, azelaic acid, sebacic acid, alkylsuccinic acids, alkenylsuccinic acids, ethylbutenylsuccinic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, ethylidenemalonic acid, isopropylidenernalonic acid, allylmalonic acid, muconic acid, alpha-hydromuconic acid, 'beta-hydromuconic acid, diglycolic acid, dilactic acid, thiodiglycolic acid, 4-amyl-2,5- heptadienedioic acid, 3-hexynedioic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-carboxy-2-methylcyclohexaneacetic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, 1,8-naphthalenedicarboxylic acid, 3-carboxycinnamic acid, 1,2-naphthalenedicarboxylic acid, 1,1,5-pentanetricarboxylic acid, 1,2,4-hexanetricarboxylic acid, 2-propyl-l,2,4-pentanetricarboxylic acid, 5-octene-3,3,6-tricarboxylic acid, 1,2,3-propanetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5- benzenetricarboxylic acid, 3-hexene-2,2,3,4-tetracarboxylic acid, 1,2,3,4-benzenetetracarboxylic acid, 1,2,3,5- benzenetetracarboxylic acid, benzenepentacarboxylic acid,

benzenehexacarboxylic acid, and the like. Copolymers of acrylic acid with an olefinically unsaturated monomer such as butadiene, styrene, ethyl acrylate, vinyl halide, and the like also can be employed. In addition, the dimerized and trimerized unsaturated fatty acids of, for example, linoleic acid, oleic acid, linolenic acid, undecylcnic acid, and the like are useful. Polycarboxylic acids which have melting points below about 250 C. are desirable; the hydrocarbon dicarboxylic acids possessing melting points below about 200 C. are preferred.

In another preferred embodiment the invention is directed to novel curable, partially cured, and cured compositions comprising the epoxy ether and polycarboxylic acid anhydride in such relative amounts so as to provide from about 0.1 to about 4.0 carboxy groups of the polycarboxylic acid anhydride per epoxy group of the epoxy ether, and preferably from about 0.8 to about 2.5 carboxyl groups per epoxy group. It should be noted that by the expression carboxyl groups of the polycarboxylic acid anhydride is meant the carboxyl groups which would be contained by the corresponding polycarboxylic acid. For example, succinic anhydride does not possess any carboxyl groups per se; however, the corresponding polycarboxylic acid is succinic acid which contains two free carboxyl groups. Thus, succinic anhydride has two carboxyl groups as applied in the above expression. In different language, by the expression carboxyl groups of polycarboxylic acid anhydride is meant the carboxyl groups contained in the hydrated polycarboxylic acid anhydride.

Illustrative polycarboxylic acid anhydrides include the aliphatic, aromatic, and cycloaliphatic acid anhydrides. The preferred anhydrides are the dicarboxylic acid anhydrides and preferably the hydrocarbon dicarboxylic acid anhydrides which include, for example, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, maleic anhydride, chloromaleic anhydride, dichloromaleic anhydride, citraconic anhydride, isocitraconic anhydride, glutaric anhydride, adipic anhydride, succinic anhydride, itaconic anhydride, heptylsuccinic anhydride, hexylsuccinic anhydride, methylbutylsuccinic anhydride, methyltetrahydrophthalic anhydride, n-nonenylsuccinic anhydride, octenylsuccinic anhydride, pentenylsuccinic anhydride, propylsuccinic anhydride, 4-nitrophthalic anhydride, 1,2-naphthalic anhydride, 2,3-naphthalic anhydride, 1,8-naphthalic anhydridc, tetrabromophthalic anhydride, tetraiodophthalic anhydride, lower alkyl substituted bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methylbicyclo[2.2.l]hept-2-ene-2,3-di- .carboxylic anhydride, and the like. Mixtures of anhydrides, polymeric anhydrides or mixed polymeric anhydn'des of sebacic, adipic, pimelic, cyclohexane-1,4-dicarboxylic, terephthalic and isophthalic acids are also useful as modifiers in the preparation of the novel compositions. Acid dianhydrides such as 1,2,4,S-benzenetetracarboxylic dianhydride likewise are effective modifiers. Polycarboxylic acid anhydrides which have melting points below about 250 C. are satisfactory; those anhydrides possessing melting points below about 200 C. are preferred.

In a further preferred embodiment, the invention is directed to novel curable, partially cured, and cured compositions comprising the epoxy ether and polyol in such relative amounts as provide from about 0.1 to about 2.0 hydroxyl groups, i.e., OH groups, of said polyol per epoxy group of said epoxy ether, and preferably from about 0.2 to about 1.0 hydroxyl group per epoxy group. By the term polyol, as used herein including the appended claims, is meant an organic compound having at least two hydroxyl groups, which are alcoholic hydroxyl groups, phenolic 'hydroxyl groups, or both alcoholic and phenolic hydroxyl groups. The term polyol preferably encompasses the polyhydric alcohols and the polyhydric phenols.

Illustrative of the polyols contemplated include, for example, the aliphatic and cycloaliphatic polyhydric alcohols, e.g., ethylene glycol, diethylene glycol, the polyethylene glycols, propylene glycol, the polypropylene glycols, the polyethylenepolypropylene glycols, trimethylene glycol, the butanediols, the butenediols, the pentanediols, the pentenediols, 2-ethyl-l,3-hexanediol, the hexenediols, 2- methoxy-2,4-dimethyl-1,S-pentanediol, 12,13-tetracosanediol, polyglycerol, 1,1,1-trimethylolpropane, pentaerythritol sorbitol, the polyvinyl alcohols, the octenediols the cyclopentanediols the cyclohexanediols, the lower alkyl substituted cyclohexanediols, inositol, trimethylolbenzene; and the polyhydric phenols, e.g., resorcinol, catechol, pyrogallol, hydroquinone, the dihydroxytoluenes, dihydroxyxylene, bis(4 hydroxyphenyl) 2,2-propane, bis(4-hydroxyphenyl)methane, 1,9-naphthalenediol, the polyhydric phenolformaldehyde condensation products, and the like. The alkylene oxide adducts, e.g., ethylene oxide, propylene oxide, etc., of polyhydric alcohols or polyhydric phenols such as those illustrated above also are highly suitable. Polyols having melting points below about 250 C. are desirable; those polyols having melting points below about 200 C. are preferred.

A further preferred embodiment of the invention is directed to novel curable, partially cured, and cured compositions comprising the epoxy ether and polycarboxy polyester in such relative amounts as provide from about 0.1 to about 2.0 carboxyl groups of said polycarboxy polyester per epoxy group of said epoxy ether, and preferably from about 0.3 to about 1.2 canboxyl groups per epoxy group. By the term polycarb oxy polyester, as used herein including the appended claims, is meant a polyester which contains at least two carboxyl groups in the average molecule. The polycarboxy polyesters can be prepared by known condensation procedures, employing mol ratios favoring greater than equivalent amounts of polycarboxylic acid or polycarboxylic acid anhydrides with relation to the polyhydric alcohol. More specifically, the amount of polycarboxylic acid or polycarboxylic acid anhydride which is employed in the esterification reaction should contain more carboxyl groups, collectively, than are required to react with the hydroxyl groups contained in the amount of polyhydric alcohol so that the resulting esterified product, i.e., polycarboxy polyester, contains at least two free canboxyl groups in the average polycarboxy polyester molecule. The polycarboxylic acids, polycarboxylic acid anhydrides, and polyols which can be employed in the preparation of the polycarboxy polyesters have been illustrated previously. The polycarboxy poly esters can be obtained by condensing, in accordance with known procedures, a polyhydric alcohol and a polycarboxylic acid or a polycarboxylic acid anhydride. This condensation reaction may be conducted, for example, by heating the reactants to a temperature within the range from C. to 200 C. with or without an acidic catalyst. Water formed by the condensation reaction may be removed by distillation. The course of the reaction may be followed by making acid number determinations and the reaction can be stopped when a suitable polycarboxy polyester has been obtained.

A still preferred embodiment is directed to curable, partially cured, and cured compositions comprising the epoxy ether and a polyfunctional amine in such relative amounts so as to provide from about 0.2 to about 5.0 amino hydro gen atoms of the polyfunctional amine per epoxy group of the ether, and preferably from about 0.8 to about 2.0 amino hydrogen atoms per epoxy group. By the term, poly-functional amine, as used herein including the appended claims, is meant an organic amine having at least two active amino hydrogen atoms which can be on the same nitrogen atom or on dilferent nitrogen atoms.

Among the polyfunctional amine subclasses contemplated include the aliphatic amines, aromatic amines, aralkyl amines, cycloaliphatic amines, alkaryl amines, aliphatic polyarnines including polyalkylene polyamines, amino-substituted monohydric and polyhydric aliphatic alcohols and phenols, polyarnides, addition products of polyamines and low molecular weight epoxides containing oxirane oxygen linked to vicinal carbon atoms, and others.

Illustrative polyfunctional amines include, for example,

methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, Z-ethylhexylamine, 3-propylheptylamine, aniline, o-hydroxyaniline, m-toluidine, 2,3-xylidine,

mesidine,

benzylamine, phenethylamine, l-naphthylamine, meta-,

ortho-,

and para-phenylene-diamines, 1,4-naphthalenediamine, 3,4-toluenediamine, cyclopentylamine, cyclohexylamine, p-menthane-l,8-diamine, Z-aminoethanol, 2-aminopropanol, 3-aminobutano1, 1,3-diamino-2-propanol, Z-aminophenol, 3-aminophenol, 4-aminophenol, 2,3-diaminoxylenol, 4,4'-methylenedianiline, ethylenediamine, propylenediarnine, butylenediamine, pentylenediamine, hexylenediamine, octylenediamine, nonylenediamine, decylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, and the like.

The polyamides, i.e., those having an average molecu lar weight range from about 300 to about 10,000, include condensation products of polycarboxylic acids, in particular, hydrocarbon dicarboxylic acids, such as malonic acid, succinic acid, glutaric acid, adipic acid, dilinoleic acid, and the like, with polyamines, particularly diamines, such as ethylenediamine, propylenediamine, butylenediamine and the like, are also useful.

Other illustrations of polyfunctional amines are the addition products of polyamines, in particular, diamines and triarnines and epoxides containing oxirane oxygen linked to vicinal carbon atoms, such as ethylene oxide, propylene oxide, butadiene dioxide, diglycidyl ether, epoxidized soybean oil, epoxidized safflower oil, and polyglycidyl polyethers of polyhydric phenols which result, such as those from the reaction of, for example, polyhydric phenols and epichlorohydrin. Particularly useful polyfunctional amines are the monoand polyhydroxyalkyl polyalkylene polyarnines which are preferably derived from the reaction of ethylenediamine, propylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, and the like, with ethylene oxide, propylene oxide, and the like. This reaction can be conducted under pressure at temperatures of 50 C. to 55 C. to boiling in the absence of solvents or in the presence of water or an alcohol. However, the reaction is more advantageously carried out at temperatures below 40 C. and preferably below 35 C. Without pressure. The amines so produced include the hydroxyalkyl-substituted alkylene polyamines such as N-hydroxyethylethylenediamine,

N,N-bis hydroxyethyl ethylenedi amine, N,Nbis (hydroxyethyl diethylenetriamine, N,Nbis hydroxyethyl diethylenetriamine, N,N"-bis (hydroxyethyl) diethylenetriamine, N-hydroxypropyidiethylenetriarnine,

N,Nbis (hydroxypropyl) diethylenetriamine, N,N-bis (hydroxypropyl -diethylenetriamine, N-hydroxyethylpropylenediamine,. N-hydroxyethyldipropylenetriamine,

N,Nbis hydroxyethyl -dispropylenetriamine, N,Nbis (hydroxyethyl dipropylenetriamine, tris hydroxyethyl triethylenete tramine,

and the like.

Other polyfunction amines can be prepared from known procedures by the addition reaction of polyglycidyl polyethers of polyhydric phenols and polyamines, in particular, polyalkylene polyamines. Of particular importance in forming these epoxide polyamine adducts are the di lycidyl diethers of dihydric phenols such as for example, the homologues of dihydroxydiphenylmethanes singly or mixed and the dihydroxydiphenyldimethylmethanes singly or mixed. Mixtures of diglycidyl diethers of dihydric phenols can be prepared by reacting epichlorohydrin with a dihydric phenol using a molar excess of epichlorohydrin over the theoretical molar requirement. Substantially pure cuts of the diglycidyl diethers then can be obtained by fractional distillation under reduced pressure, for example. Illustratively, the polyfunctional amine, i.e., the epoxide-polyamine adduct, itself can be prepared by mixing the diglycidyl diether of a dihydric phenol with a polyalkylene diamine such as diethylenetriamine, dipropylenetriamine, and the like, bringing to an elevated temperature for example, up to about 200 C. and maintaining at such an elevated temperature for a period of from about 4 to 5 hours. Alternatively, as an illustration, polyfunctional amines can be prepared by adding a diglycidyl diether of a dihydric phenol to a polyalkylene polyamine over a period of time, e.g., from about three to four hours, while maintaining the reaction mixture at an elevated temperature, for example up to about 200 C. and subsequently adding a dihydric phenol.

Examples of still other polyfunctionai amines suitably adaptable for use in the present invention include, among others, heterocyclic nitrogen compounds such as piperazine, 2,5-dimethylpiperazine, and the like; aminoalkylsubstituted heterocyclic compounds such as N-(arninopropyDmorpholine, N(aminoethyl)morpholine, and the like; amino-substituted heterocyclic nitrogen compounds such as melamine, 2,4-diamino-6-(aminoethyl)pyrimidine, and the like; dimethylurea, guanidine, 4,4-sulfonyldianiline, 3,9-bis(aminoethyl)spirobimetadioxane, hexahydrobenzamide; and others.

Polyfunctional amines formed by the addition of amines to unsaturated compounds such as acrylonitrile, ethyl acrylate, propyl acrylate, butyl crotonate, and the like are suitable.

The invention also contemplates the modification of the properties and characteristics of the partially cured and fully cured compositions (resins) set forth previously in the discussion of the five previous preferred embodiments. Special and highly desirable eifects can be imparted to the partially cured and fully cured compositions by incorporating a second active organic hardener (hereinafter termed modifier) into the curable composition comprising the epoxy ether and major active organic hardener (i.e., polycarboxylic acid, polycarboxylic acid anhydride, polyol, polycarboxy polyester, and the like).- The proportions of modifier to major active organic hardener are such that the number of reactive groups contained by an amount of the modifier with relation to the number of reactive groups contained by an amount of the major active organic hardened will be in a ratio that is less than one. It is to be understood that the term reactive groups pertains to groups which are reactive with the epoxy groups contained in the epoxy ether. For instance, to a curable composition comprising the epoxy ether and polycarboxylic acid, there can be added an amount of a modifier, e.g., polycarboxylic acid anhydride, polycarboxy polyester, polyol, etc., such that the ratio of reactive groups contained by the modifier with respect to the carboxyl groups contained by the polycarboxylic acid is less than one. On this basis the modifier can be considered to be the minor component in relation to the polycarboxylic acid. As a second illustration, if the curable composition comprises the epoxy ether and polyol, an amount of modifier, e.g., polycarboxylic acid, polycarboxy polyester, polycarboxylic acid anhydride, polyisocyanate, polythiol, etc., can be added to said curable mixture such that the ratio of the reactive groups contained by the modifier with respect to the hydroxyl groups contained by the polyol is less than one. Again it will be noted that the modifier is the minor component with respect to the polyol. The modifiers which can be employed are those illustrated previously in the discussion of polycarhoxylic acids, polycarboxylic acid anhydrides, polyols, polycarboxy polyesters, etc.

A further highly preferred embodiment is directed to curable and partially cured compositions (thermosetting intermediate reaction products that are viscous liquids or solids) comprising the epoxy ether and an active organic hardener, with or Without a modifier, said compositions being dissolved in an inert normally-liquid organic medium such as xylene, methyl isobutyl ketone, butyl acetate, ethyl acetate, toluene, amyl acetate, and the like. The compositions dissolved in the above exemplary list of organic media can be used as, for example, surface coating which can be subsequently heat cured to hard, tough, scratch-resistant coatings.

The proportion of partially cured resin, i.e., thermosetting intermediate reaction products, or to organic media will depend on various factors such as the particular mixture being cured, the degree of extent of the partial cure, the particular organic medium employed, and other considerations. In general, a solution comprising from about to about 90 Weight percent of the partially cured resin, based on the total weight or partially cured resin and organic medium, is suitable; from about 40 to 70 weight percent of the partially cured resin, based on the total weight or partially cured resin and organic medium, is preferred. Moreover, the uncured compositions can be dissolved in the organic media exemplified above and applied to surfaces and subsequently heat cured to form hard, tough coatings. Should the solution comprising the uncured composition or partially cured composition tend to run when applied to the surface, a conventional wetting agent and/or thixotropic agent can be added to the solution mixture to ensure a more uniform coating on the surface.

In yet another preferred embodiment, the invention is directed to the homopolymerization of the epoxy ether in the presence of a catalyst at a temperature in the range of from 25 C. to about 300 C. preferably from about 25 to about 250 C., to produce homopolymeric products. It is generally suitable to add the catalyst to the monomer which is maintained at temperature in the range from about 10 C. to 25 C. Agitation of the monomer composition prior to, during, and after the incorporation of the catalyst is desirable. Catalyst concentrations and polymerization temperatures are believed to affect the polymerization rate, the higher concentrations and temperatures promoting faster polymerization than the lower ones. Catalyst concentrations can be varied over a broad range and can be selected on the basis of polymerization desired and the polymerization temperature to be used. It has been found that catalyst concentrations from about 0.005, and lower, to 15 and higher, Weight percent, preferably from about 0.01 to 5 Weight percent, based on the weight of the epoxy ether monomer are advantageous in forming useful homopolymeric products. After the reaction mixture has been formed, the mixture is heated to a temperature in the range, for example, of from about 50 C. to 160 C. to effect a gel. After gelation, a post cure can be carried out at a temperature, for example, in the range of from C. to 250 C. for a period of time ranging, for example, from about 30 minutes to 24 hours, and longer. It is pointed out that the reaction time will vary depending on factors such as temperature, catalyst, catalyst concentration, and the like. The polymeric products produced are hard, infusible products suitable for use in castings which can be machined to make a variety of useful products.

Basic and acidic catalysts which can be employed in the compositions include, for example, the metal halide Lewis acids, e.g., boron trifluoride, aluminum chloride, zinc chloride, stannic chloride, ferric chloride, boron trifluoride-piperidine complex, boron trifiuoride-l,6-hexa nediamine complex, boron trifluoride-monoethylamine complex, boron triiiuoride-dimethyl ether complex, boron trifiuoride-diethyl ether complex, boron trifiuoride-dipropyl ether complex, and the like; the strong mineral acids; e.g., sulfuric acid, phosphoric acid, polyphosphoric acid, perchloric acid, and the like; the saturated aliphatic hydrocarbon sulfonic acids and the aromatic hydrocarbon sulfonic acids, e.g., ethylsulfonic acid, propylsulfonic acid, benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, lower alkyl substituted-benzenesulfonic acid, and the like; the alkali metal hydroxides, e.g., sodium hydroxide, potassium hydroxide, and the like; the amines, e.g., alpha-methylbenzyldimethylamine, dimethylethylamine, triethylamine, tripropylarnine, trimethylammonium hydroxide, and the like. When the catalyst and monomers are immiscible, the catalyst can be added as a solution in an inert normally-liquid organic medium. Typical media for the catalyst include the organic ethers, e.g., diethyl ether, dipropyl ether, and the like; the organic esters, e.g., methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, and the like; the organic ketones, e.g., acetone, cyclohexanone, methylcyclohexanone, and the like.

In another preferred embodiment the invention is directed to the preparation of Valuable varnishes which are obtained by the reaction of the epoxy ether with aliphatic monocarboxylic acids, at elevated temperatures, e.g., about 100 C. to 200 C., for a period of time ranging from 0.5 to 10 hours, and longer, followed by homopolymerizing the resulting reaction product (which contains residual or free epoxy and hydroxyl group) with a catalyst such as those described previously, preferably at a temperature in the range of from about 25 C. to 200 C., to thus produce high molecular weight polymeric products commoniy known to the art as a varnish. The amounts of aliphatic monocarboxylic acid and epoxy ether employed are such so as to provide from about 0.3 to about 0.7 carboxyl group of monocarboxylic acid per epoxy group of epoxy ether. The unsaturated aliphatic monocarboxylic acids are preferred. Illustrative acids include hexanoic acid, caprylic acid, lauric aid, capric acid, myristic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, licanic acid, ricinoleic acid, hexenoic acid, hexadieneoic acid, octenoic acid. Acids derived from natural sources such as castor oil, dehydrated castor oil, coconut oil, cottonseed oil, oiticica oil, perilla oil, olive oil, safflower oil, sardine oil, soyabean oil, tall oil, tung oil, and the like are advantageous to employ both from an economic standpoint and since highly useful varnishes result from the process. If desired, the reaction between the epoxy ether and the aliphatic monocarboxylic acid can he eifected in the presence of a catalyst such as those described previously, and also, the reaction can be conducted in the presence of an inert normally-liquid organic medium. Suitable media include, for instance, the aromatic hydrocarbon, e.g., benzene, toluene, xylene, and the like; the saturated aliphatic and cycloaliphatic hydrocarbons, e.g., hexane, hetpane, cyclopentane, cyclohexane, lower alkyl substituted cyclohexane, and the like; the oxygenated organic compounds, e.g., ethyl acetate, butyl acetate, amyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, diisopropyl ether, and the like.

The homopolymerizing of the reaction product which contains residual or free epoxy and hydroxyl groups can also be effected, if desired, in the presence of an inert normally-liquid organic medium such as those illustrated supra. The progess of the homopolymerization reaction can be observed by determining the relative viscosity of samples drawn from the reaction mixture. In this manner it is possible to produce partially polymerized compositions or essentially complete polymerized compositions. The polymerized compositions of this embodiment generally are obtained as very viscous products. These polymerized compositions can be classified as drying compositions or non-drying compositions. The former are those which contain ethylenic unsaturation whereas the latter are saturated compositions. Both the drying and non-drying compositions are useful as modifiers for coating resins such as phenol-formaldehyde resins, melamineformaldehyde resins, alkyld resins, and the like. These compositions are outstanding as modifiers because they have a wide range of compatability, they impart improved caustic, water, and chemical resistance to the resin coatings they are modifying, and they impart improved flexibility and toughness. The drying compositions are capable of drying or curing to excellent protective coatings with or without the application of heat. It is generally desirable to employ various metallic salts of organic compounds known to the art as driers, to accelerate the drying process. The drying can be accomplished at temperatures in the range of from about to about 250 C. for a period of time sufiicient to produce the desired property in the resin. The concentration of the drier compound can range from about 0.001 to abot 5.0 weight percent, and higher, based on the Weight of the drying compound (polymer). Suitable driers include soluble compounds containing heavy metals, e.g., cobalt, lead, manganese, calcium, zinc, iron, and the like. Examples of such driers include cobalt naphthenate, lead octanoate, and the like. The drying compositions can be treated in the various ways familiar to the varnish and paint industries to produce special or advantageous eifects.

In a still further preferred embodiment valuable varnish compositions can be obtained by the reaction of the epoxy ether with polyols, at a temperature in the range of from about 25 to 250 C., for a period of time ranging from about 0.5 to 10.0 hours, and longer, followed by partial or essentially complete esteriflcation of the fusible, polymeric polyhydric product with an aliphatic monocarboxylic acid, at elevated temperatures, to produce high molecular weight polymeric products (varnishes) which may contain residual or free hydroxyl groups. The proportions of polyol and epoxy ether employed are such as to provide from about 0.5 to about 1.5 hydroxyl groups of polyol per epoxy group of epoxy ether. The polyols and aliphatic monocarboxylic acids which can be employed have been illustrated previously. The use of catalysts and solvents, if desired, have also been discussed supra.

As further embodiments, valuable thermoset resins can be prepared from curable compositions comprising the epoxy ether, an active organic hardener(s), and other polyepoxides such as limonene dioxide, 4-vinylcyclohexene dioxide, 'dicyclopentadiene dioxide, divinylbenzene dioxide, 3,4-epoxy-6-methylcyclohexylmethyl 3,4-epoxy- 6 methylcyclohexanecarboxylate, diethylene glycol bis (3 ,4-epoxycyclohexanecarboxylate) bis (2,3-epoxycyclopentyl) ether, bis(3,4-epoxycyclohexylmethyl) pimelate, 1,1,1-trimethylolpropane tris(3,4-epoxycyclohexanecarboylate) the polyglycidyl polyethers of poly-hydric phenols, and the like. The curing of these novel curable compositions has been disclosed supra.

The cured resins of the invention vary from soft and flexible to hard and rigid products, depending upon the proportion, the functionality, and the chain length of the active organic hardener(s) employed. These resins are insoluble in many of the organic solvents. The hard, infusible, rigid, thermoset resins can be machined to desired shapes and configurations, and they can be polished to provide appealing finishes. The novel compositions, as indicated throughout the specification, are highly useful and valuable in fields such as the coatings, laminating, molding encapsulation, etc., arts.

In the following illustrative examples the examination and description of the resins were conducted at room temperature, e.g., about 24 C. The Barcol hardness values were determined by the use of Barcol Impressor GYZJ-934l at a temperature of 25 C.

EXAMPLE 1 In a reaction flask, 1425 grams of hydroxydihydrodicyclopentadiene, 627 grams of weight percent dicyclopentadiene, and 82 grams of boron trifluoride-etherate are heated at 70-S0 C. for 6 hours. The reaction mixture is cooled to room temperature, washed with 800 milliliters of hot water, then washed with 800 milliliters of salt water. The resulting organic phase is separated from the washed reaction product mixture and dewatered by heating under reduced pressure. After filtering the organic phase through cheese cloth, followed by distillation, there is obtained 779 grams of dicyclopentadiene, 945 grams of hydroxydihydrodicyclopentadiene, and 211 grams of bis(tricyclo[4.3.0.1 ]-7-decen3-yl) ether, Said ether has the following properties:

Boiling point--169174 C. at 2 millimeters Hg Refractive indexn 30/ D 15348-45364 EXAMPLE 2 To grams of bis(tricyclo[4.3.0.1 ]-7-decen-3-yl) ether which is maintained with stirring at 40 (2., there is added dropwise, over a period of 90 minutes, 273 grams of 27.8 weight percent solution of peracetic acid in ethyl acetate. After an additional two hours and 45 minutes, the reaction is 99 percent complete as indicated by analysis for unreacted peracetic acid. The reaction mixture is added to 500 grams of ethylbenzene which is refluxing under reduced pressure. Ethyl acetate, excess peracetic acid, acetic acid, and ethylbenzene is continuously removed overhead. The residue is freed of volatiles by heating at 90 C. for 15 minutes under a pressure of 4.0 millimeters Hg. The product, bis(3- oxatetracyclo[4.4.0.1' ".0 ]undec-8-yl), ether, weighs 126 grams and has the following properties:

Purity-87 percent (by hydrogen bromide analysis for epoxide) Iodine number-0.8

Acidity (as peracetic acid)--0.8O percent EXAMPLES 3-7 Bis(3 oxatetracyclo[4.4.0.1 .0 ]undec 8 yl) ether (0.8 gram) and various hardening agents were mixed in test tubes and heated until homogeneous. The mixtures were cured for 18 hours at C. and 6 hours at C. The pertinent data and results are set forth in Table I below.

13 14 Table I EXAMPLES 23-29 Exmple Harden gg Resin Description Bis(3 -oxatetracyclo[4.4.0.1' .0 ]undec-8-y1) ether, 5 maleic anhydride and nimethylolpropane were mixed in gigggig fifffi: 8 g gl various proportions and the mixtures were heated and 13513;? jannehydgggggifi 8.57 5 1 1 11, Barcol, 47. stirred until homogeneous. The mobile rmxtures were 11011 e. Adduc't Pf fih gi g 6 Tough, Bmol, 1H3. poured into molds and were cured for three hours at 120 S11 C e 2 a 53 mom g 10 C., so: hours at 160 C., and four hours at 200 C. The

following data were observed:

Table IV Formulation Trimethylol- Heat Distor- Propane tion, C.

Maleic Anhydride Gel time, Example Hydroxyl Hours at Barcol Bis(3-oxatet1"aey- Group 120 C. Cure@ Oure@ clOMAdOJg Qg -fl- CGarboxyl Grams EPer 425301165, 11 24 un ecrou ether, gra ms Grams Per (153g 260 Epoxy Group 111 23.7 0.8 5.3 0.2 34 g 7 41 83 213 10 5.1 1.0 0.9 0.2 2.5 42 122 231 17.0 5.8 1.2 1.3 0.3 2- 42 102 205 17. 2 6. 5 1. 4 1.3 0. 3 42 208 201 16. 6 7. 2 1. 6 1. 2 0. a 45 257 203 10. 1 7. 7 1.8 1. 2 0. 3 48 258 270 15. 5 s. 4 2. 0 1. 1 0. 3 48 240 270 EXAMPLES 8-16 EXAMPLE Bis(3 oxatetracyclo[4.4.0.1 .0 ]undec 8 yl) The following formulation: ether (1.83 grams), maleic anhydride, and 1,1,1-trimeth- I 2 4 y p p were mixed in various proportions in test 5.8eihgerfams b1s(3 oxatetracyclo[4.4.0.l .0 ]undec 8 yl) tubes. The mixtures were heated at 120 C. for 0.5 hour and at 160 C. for six hours. The following data 232 $3 g zg gf were observed. gr y p p Table II was mixed in a test tube and heated until homogeneous. The homogeneous mixture was cooled to 3540 C. at Male; Tri Ran-0s, Equivalents which time 1.95 grams styrene and 0.0014 gram benzoyl E 1 Ainhiymethylol- Per Epoxide Group Ch Resin tic peroxide were added. The mixture gelled after five hours amps i propane mac ens s at 50 C. and the resin was post cured for one hour at Carboxylfiydwxyl 120 C. and for two hours at 160 C. The resin was fairly tough and had a Barcol hardness of 56. 0.05 0. 025 0.1 0.05 v' 1 25 3.2 31 1 5 H air EXAMPLE 31 0. 0.80 0.20 1-6 g s Barcol, A mixture is prepared from bis(3 oxa-tetracyclo g g 8,2 .0.g fl flimdec-tlg l)1 gtherb and adipic acid in a amoun so as o provi e car oxy group per epoxy Barcol 50 group. The resulting mixture is heated to 120 C. for a 7 0- 5 3. 5 5 Tough, Barwl, period 10 minutes, and upon cooling to room temperature, 2,0 25 M (L5 Tou'gh i.e., approximately 25 C., a thermosetting product is obtamed. The resulting product is dissolved 1n methyl 1S0- butyl ketone at 100 C., and an iron panel or strip is EXAMPLES 17-22 dipped into the resulting solution. The iron panel subseuentl is removed from this solution is air dried for 15 B186 l" -9' F 21mm; and is baked at 160 0. foi' 2 hours. A grails) ai i and type 2 22??? r 3? 3 2: coating is observed on that portion of the dipped iron test m e :Vere d 111 t rth panel. The resulting coating on the panel is glossy and W hours' The Perm-lent a a an res ts are Se 0 tough. The coating displays excellent adhesion to the in Table In below. paneL Table 111 EXAMPLE 32 A mixture is prepared from bis(3-oxatetracyclo- H d W ht, Re 111 Example ar ener r iins charact erisucs [4.4.0.1 Q.0 ]undec-8-yl) ether and phthahc annydrlde in amounts so as to provide 1.0 carboxyl group per epoxy 17 Methylated maleic acid adduct 0.9 Soft solid. group. The resulting mixture is heated to 120 C. for a g g gg ffigg fi (L7 strong tough, period of 5 minutes, and upon cooling to room tempera- Barcol, 40. ture, i.e., approximately 25 C., a thermosetting product gg g f gg gggg f 5:2 233%; 12m is obtained. The resulting product is dissolved in butyl 1 acetate at C., and an iron panel or strip is dipped fig gg gg gg ggf $2 i fig fg into the resulting solution. The iron panel is removed cerol. Acid equiva1ent, 134. almost immediately from this solution, is allowed to air 22 Maleanhydride+Adiplcacld figf ffd dry for 15 minutes, and subsequently is baked at C. for 15 minutes. A thin coating is observed on that Amixture 010.4 gram maleic anhydride and 0.14 gram adipic acid. 75 Portion of the pp Iron p The resulting coating 15 on the panel is hard and tough. The coating displays excellent adhesion to the panel.

EXAMPLE 3 3 Bis(3 oxatetracyclo[4.4.0.1 .0 ]undec-8-yl) ether and dehydrated castor oil acid are admixed in amounts so -as to provide 0.5 carboxyl group of said acid per epoxy group of said ether. The resulting admixture then is heated for 0.7 hour at 180 C. to give a viscous product mixture which contained residual or free epoxy groups and hydroxyl groups. This viscous product mixture subsequently is charged to a round-bottorned flask which is fitted with an air stirrer, nitrogen purge line, thermometer, and dropping funnel. Sufficient xylene solvent is added to give a 90 weight percent solution and the temperature of the resulting admixture is brought to about 55 to 60 C. An amount of stannic chloride (0.3 weight percent based on the weight of said viscous product mixture) contained as a solution in ethyl acetate is then added dropwise to said admixture over a period of approximately 45 minutes. As the polymerization proceeds, suflicient xylene is added thereto to facilitate stirring. The solids content of the resulting solution is about 55 weight percent. To the resulting high molecular weight polymeric product mixture (varnish), a Parkerized steel panel is dipped therein. The resulting coated panel is air-dried for 30 minutes and is baked at 170 C. for 30 minutes. The coated panel resistance to boiling Water (one hour) and caustic (20 percent NaOH for 20 minutes) is excellent.

EXAMPLE 34 Bis(3-oxatetracyclo[4.4.0.l .0 ]undec 8 yl) ether and soya bean oil acid are admixed in amounts so as to provide 0.4 carboxyl group of said acid per epoxy group of said ether. The resulting admixture then is heated for 0.9 hour at 180 C. to give a viscous product mixture which contained residual or free epoxy groups and hydroxyl groups. This viscous product mixture subsequently is charged to a round-bottomed flask which is fitted with an air stirrer, nitrogen purge line, thermometer, and dropping funnel. Sufiicient xylene solvent is added to give a 85 weight percent solution and the temperature of the resulting admixture is brought to about 50 to 60 C. An amount of boron trifluoridediethyl ether complex (0.2 weight percent of boron trifluoride based on the Weight of said viscous product mixture) contained in excess diethyl ether is then added dropwise to said admixture over a period of approximately 30 minutes. As the polymerization proceeds, sufiicient xylene is added thereto to facilitate stirring. The solids content of the resulting solution is about 50 weight percent. To the resulting high molecular weight polymeric product mixture (varnish), a 'Parkerized steel panel is dipped therein. The resulting coated panel is air-dried for 20 minutes and is baked at 175 C. for 30 minutes. The coated panel resistance to boiling water (one hour) and caustic (20 percent NaOH for 20 minutes) is excellent.

EXAMPLE 35 thylene glycol (45 grams), toluene (400 grams), and stannic chloride (2.0 grams) are charged to a reaction flask which is fitted with an air stirrer, thermometer, and dropping funnel. The resulting mixture is heated to about 100 C. and an amount of bis(3-oxatetracyclo[4.4.0.1 .0 ]undec-S-yl) ether (suflicient to provide one epoxy group per hydroxyl group of said ethylene glycol).is added dropwise thereto over a period of 30 minutes. The reaction mixture subsequently is allowed to cool to about 75 C., and thereafter ice Water is added to the reaction mixture, with stirring, to thus form a heterogeneous polymer-solvent-Water mixture. The liquid portion is decanted into a separating funnel and the remaining solid polymer phase is dissolved in hexanone; the resulting solution is then added to the decanted material. The resulting mixture subsequently is shaken with additional water and is allowed to stand overnight at room temperature after which time the polymer solution phase is recovered. The polymer solution phase is added to a two-liter flask to which are attached a distillation head, a vacuum pump, and a heating mantle. The solvents (cyclohexanone and toluene) are removed by heating at elevated temperatures and under reduced pressure. On cooling, there is obtained a polymeric polyhydric solid product. This product, dehydrated castor oil acid in an amount to cause essentially complete esterification, and xylene then are charged to a two-liter flask fitted with a stirrer, a nitrogen purge line, a thermometer, a distillation head, and a heating mantle. The mixture is heated to about 240 C. and is maintained thereat for approximately 2 hours during which period of time the water which is formed from esterification is removed at the still head as an azeotrope with xylene. The reaction mixture is allowed to cool to about 120 C., and sufiicient xylene is added to afford a varnish solution containing about 75 weight percent non-volatiles.

To 100 parts by weight of the above said varnish solution there is added 15 parts by Weight of xylene. To this resulting solution there is added 0.015 part by Weight of cobalt naphthenate. Subsequently, a black iron panel is dipped in the varnish solution. The panel is removed almost immediately from said solution, is allowed to air dry for 30 minutes, and subsequently, is baked at 160 C. for 30 minutes. The resulting coating on the panel is glossy, tough, and resistant to cracking on continual bending (over degree bends) of the panel. The coating displayed excellent adhesion and excellent resistance to caustic.

Although the invention has been illustrated by the preceding examples, the invention is not to be construed as limited to the materials employed in the above exemplary examples, but rather, the invention encompasses the generic area as hereinbefore disclosed. Various modifications and embodiments of this invention can be made without departing from the spirit and scope thereof.

What is claimed is:

1. Bis(3 oxatetracyclo[4.4.0.1' .0 ]undec 8 yl) ether.

2. A process for the production of bis(3-oxatetracyclo- [4.4.0.1 .0 ]undec-8-yl) ether which comprises reacting bis(tricyclo[4.3.0.1 ]-7-decen-3-yl) ether with an organic peracid at a temperature in the range from about 0 C, to about C. and recovering the ether produced.

3. The homopolymer of bis(3 oxatetracyclo- [4.4.0.1 .O ]undec-8-yl) ether.

4. A process which comprises reacting bis(3-oxatetracyclo[4.4.0.l .0 ]undec-8-yl) ether with a catalyst selected from the group consisting of metal halide Lewis acids, strong mineral acids, the saturated hydrocarbon sulfonic acids, the alkali metal hydroxides, and the amines, at a temperature in the range from about 25 C. to about 250 C., for a period of time suflicient to produce a polymer.

5. A polymerizable composition comprising bis(3-oxatetracyclo[4.4.0.1' .0 ]undec-8-yl) ether and a curing amount of an active organic hardener selected from the group consisting of polycarboxylic acids, polycarboxylic acid anhydrides, polyhydric alcohols, polyhydric phenols, polycarboxy polyesters, polythiols, polyisocyanates, polythioisocyanates, polyacyl halides, and polyfunctional amines.

6. A cured, thermoset resin obtained from the composition defined in claim 5.

7. The composition of claim 5 wherein said active organic hardener is a polycarboxylic acid which is employed in an amount so as to provide from about 0.1 to about 2.0 carboxyl groups per epoxy group of said ether.

8. The composition of claim 5 wherein said active organic hardener is a polycarboxylic acid anhydride which is employed in an amount so as to provide from about 17 0.1 to about 4.0 carboxyl groups per epoxy group of said ether.

9. The composition of claim wherein said active organic hardener is a polyhydric alcohol which is employed in an amount so as to provide from about 0.1 to about 2.0 hydroxyl groups per epoxy group of said ether.

10. The composition of claim 5 wherein said active organic hardener is a polyhydric phenol which is employed in an amount so as to provide from about 0.1 to about 2.0 hydroxyl groups per epoxy group of said ether.

11. The composition of claim 5 wherein said active organic hardener is a polycarboxy polyester which is employed in an amount so as to provide from about 0.1

to about 2.0 carboxyl groups per epoxy group of said ether.

12. The composition of claim 5 wherein said active hardener is a polyfunctional amine which is employed in an amount so as to provide from about 0.2 to about 5.0 amino hydrogen atoms of said polyfunctional amine per epoxy group of said ether.

13. A cured, thermoset resin obtained from the composition defined in claim 7.

14. A cured, thermoset resin obtained from the composition defined in claim 8.

'15. A cured, thermoset resin obtained from the composition defined in claim 9.

16. A cured, thermoset resin obtained from the composition defined in claim 10.

17. A cured, thermoset resin obtained from the composition defined in claim 11.

18. A cured, thermoset resin obtained from the composition defined in claim 12.

19. Thermosetting intermediate reaction products resulting from the partial reaction of a polymerizable composition comprising bis(3-oxatetracyclo[4.4.0.l' l0 undec-S-yl) ether and a curing amount of an active organic hardener selected from the group consisting of polycarboxylic acids, polycarboxylic acid anhydrides, polyhydric alcohols, polyhydric phenols, polycarboxy polyesters, polythiols, polyisocyanates, polythioisocyanates, polyacyl halides and polyfunctional amines; said thermosetting intermediate reaction products being dissolved in an inert normally-liquid organic medium, the resulting solution comprising from about 10 to about weight percent of said thermosetting intermediate reaction products, based on the total Weight of said thermosetting intermediate reaction products and said organic medium.

20. A polymerizable composition comprising bis(3-oXatetracyclo[4.4.0.1 .0 ]undec-8-yl) ether and an aliphatic unsaturated monocarboxylic acid in amounts so as to provide from about 0.3 to about 0.7 carboxyl group of said acid per epoxy group of said ether.

21. The reaction product of the composition defined in claim 20, said product containing free hydroxyl and epoxy groups.

22. A varnish composition obtained by homopolymerizing the reaction product defined in claim 21.

23. A process for producing a fatty acid ester which contains free Vic-epoxy groups which comprises interacting bis(3-oxatetracyclo[4.4.0.1 .0 ]undec-8-yl) ether with an aliphatic monocarboxylic acid in amounts so as to provide from about 0.3 to about 0.7 carboxyl group of said acid per epoxy group of said ether.

24. A process for producing a varnish composition which comprises homopolymerizing the fatty acid ester product of claim 23.

References Cited in the file of this patent UNITED STATES PATENTS 2,543,419 Niederhauser Feb. 27, 1951 

1. BIS(3 - OXATETRACYCLO(4.4.0.1 7,1002,4(UNDEC - 8 - YL) ETHER. 